CN109096265A - 一种吡啶亚甲基香豆素类铜离子荧光探针及其制备 - Google Patents
一种吡啶亚甲基香豆素类铜离子荧光探针及其制备 Download PDFInfo
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Abstract
本发明涉及一种吡啶亚甲基香豆素类铜离子荧光探针的制备与应用，所述荧光探针，化学名称为：7‑二乙基氨基‑3‑(吡啶‑2‑亚甲基)氨基香豆素；所述荧光探针的制备包括步骤有：(1)3‑氨基‑7‑二乙基氨基香豆素与2‑吡啶甲醛在脱水剂的作用下得到中间体亚胺化合物；(2)中间体亚胺化合物在还原剂作用下得到目标荧光分子探针化合物。所述荧光探针的应用，是利用铜离子能够淬灭分子荧光探针化合物的荧光性来检测二价铜离子的存在与否。本发明探针的制备简单，反应条件温和，且后处理过程相对简单。本发明荧光探针分子在二价铜离子检测过程中表现出较高的选择性和灵敏度。
Description
技术领域
本发明属于有机荧光小分子探针领域，具体涉及的是一种香豆素衍生物铜离子荧光探针及其制备方法。
背景技术
铜元素作为人体内的一种必不可少的微量元素，是机体内蛋白质和酶的组成部分，对人体的新陈代谢起着重要作用。铜离子过多或过少，都会对身体造成重大的影响。当铜离子浓度低于1μM时，对许多生命过程(生物催化反应酶的辅酶、生物的运输过程、生物的合成)有害作用，然而，当在生物体内存在的浓度过高时，则会对一些必须酶的抑制作用、生物氧化/还原过程异常、产生神经毒性等有害作用，导致神经系统退化性疾病如：阿尔茨海默氏病，帕金森病，门克斯病，威尔逊病等等。
随着人民生活水平的提高，对自身的健康的要求也越来越高，因此对铜离子的检测要求也越来越高。小分子荧光探针由于其快速，简单，高效，高选择性，高灵敏性以及无损伤检测等特点成为广大科硏工作者的热点之一。在众多的小分子荧光探针中，香豆素类化合物具有荧光量子产率高、Stokes位移大、光物理和光化学性质可调以及光稳定性好等优点，因此近年来香豆素类荧光探针的设计、合成逐渐成为一个新兴的研究热点。
发明内容
一种用于铜离子检测的香豆素类荧光分子探针，其具有如下结构。
上述荧光分子探针的制备方法，包括如下步骤：
(1)3-氨基-7-二乙基氨基香豆素与2-吡啶甲醛在脱水剂的作用下得到中间体亚胺化合物。
(2)中间体亚胺在还原剂作用下得到荧光分子探针化合物。
进一步，步骤(1)中3-氨基-7-二乙基氨基香豆素与2-吡啶甲醛的摩尔比为1：1～1：5之间。
进一步，步骤(1)中所用的脱水剂为无水硫酸钠、无水硫酸镁、无水氯化钙、分子筛中的一种或几种。
进一步，步骤(2)中所用的还原剂为硼氢化钠、氢化铝锂、氢化钙中的一种或者几种。
上述的荧光分子探针应用于检测铜离子。
本发明的优点及其效果
本发明探针结构简单，制备过程步骤少，反应条件温和，且后处理过程相对简单。本发明荧光探针分子在铜离子的测定过程中表现出较高的选择性和灵敏度。
附图说明
图1为化合物I的1H NMR图谱；
图2为化合物I的13C NMR图谱；
图3为化合物I的紫外吸收图谱；
图4化合物I对不同金属离子Ag+、Al3+、Ba2+、Cd2+、Co2+、Cr3+、Cu2+、Fe2+、Fe3+、Hg2+、Mn2 +、Ni2+、Pd2+、Sn4+、Zn2+的响应情况。
具体实施方式
以下对本发明实施例做进一步详述：需要强调的是，本发明所述的实施例是说明性的，而不是限定性的，因此本发明并不限于具体实施方式中所述的实施例，凡是由本领域技术人员根据本发明的技术方案得出的其它实施方式，同样属于本发明保护的范围。
实施例1：中间体亚胺的合成
3-氨基-7-二乙基氨基香豆素1.16g加入30mL二氯甲烷溶液溶解，在磁力搅拌器下搅拌加入618μL吡啶甲醛，再加入2.13g无水硫酸钠，在室温下搅拌反应24小时。反应结束，过滤，用少量二氯甲烷溶液洗涤硫酸钠固体，将溶液减压蒸干，得到亚胺的粗产物(产品无需纯化直接用于下一步)。
实施例2：目标化合物I的合成
将上步得到的的粗产物加入30mL无水甲醇溶解，冰浴冷却，待溶液彻底冷却后，分批加入硼氢化钠0.57g，继续冰浴反应2小时，室温反应过夜。反应结束，将溶液减压蒸干溶剂，加入30mL蒸馏水，30mL二氯甲烷，在磁力搅拌器下搅拌溶解，将所得的水溶液直接倒入分液漏斗中，分液，水层用20ml二氯甲烷洗涤两次，合并有机相，有机相用饱和氯化钠水溶液洗涤，无水硫酸钠干燥，过滤，减压蒸馏得到粘稠状液体。将得到的粗产物硅胶柱层析，洗脱剂为石油醚：乙酸乙酯＝3:1，得到目标化合物I(0.845g，产率52.3％)。1H NMR(400MHz，CDCl3,ppm):δ8.60—8.59(m，1H)，7.67—7.63(m，1H)，7.34(d，J＝8.0，1H)，7.20—7.18(m，1H)，7.07(d，J＝8.4，1H)，6.56—6.53(m，1H)，6.30(s，1H)，5.39(s，1H)，4.47(d，J＝4.0，2H)，3.36(q，J＝7.2，4H)，1.17(t，J＝7.2，6H)；13C NMR(400MHz，CDCl3,ppm):δ160.30，157.69，150.45，149.36，136.85，125.97，122.32，121.23，49.16，12.47；MS(ESI):C19H21N3O2,([M+H]+)测量值324.2(理论值324.17)。
实施例3：化合物紫外光谱和荧光光谱的测定
将化合物I溶于DMSO配制成浓度为2mM的溶液，并于4℃下保存；紫外可见光谱和荧光光谱均在缓冲溶液(25mM HEPES，0.1M NaClO4，pH＝7.4，5％(V/V)DMSO)中测定。在2ml的缓冲液中加入2uL的荧光探针I的溶液，混合均匀，分别测定其紫外可见光谱和荧光光谱。同时分别加入等量的不同的金属离子测定其荧光性能的变化。
化合物I的紫外吸收光谱从如图3所示。在模拟生理环境下(25mM HEPES，0.1MNaClO4，pH＝7.4，5％(V/V)DMSO)没有加入铜离子前化合物I最大吸收峰在226nm，在265和389nm处分别有两吸收峰。当向溶液中加入铜离子后226nm处的吸收峰明显增强，265nm处的吸收峰完全消失，389nm处的吸收峰移动到433nm并且吸收强度也有明显的增强。这说明溶液中化合物I与铜离子形成了一种配合物。
从图4可以看出化合物I与Ag+、Al3+、Ba2+、Cd2+、Co2+、Cr3+、Cu2+、Fe2+、Fe3+、Hg2+、Mn2+、Ni2+、Pd2+、Sn4+、Zn2+等离子并无明显的荧光变化，而Cu2+引起荧光淬灭效果最为明显，这说明化合物I对铜离子具有良好的选择性。
Claims (6)
1.一种用于铜离子检测的香豆素类荧光分子探针化合物，其特征在于：所述的荧光分子探针化合物具有如下化学结构：
2.权利要求1所述荧光分子探针的制备方法，包括如下步骤：
(1)3-氨基-7-二乙基氨基香豆素与2-吡啶甲醛在脱水剂X的作用下得到中间体亚胺化合物(II)。
(2)中间体亚胺化合物(II)在还原剂Y作用下得到荧光分子探针化合物(I)。
3.权利要求2所述荧光分子探针的制备方法，其特征在于：步骤(1)中3-氨基-7-二乙基氨基香豆素与2-吡啶甲醛的摩尔比为1：1～1：5之间。
4.权利要求2所述荧光分子探针的制备方法，其特征在于：步骤(1)中所用的脱水剂X为无水硫酸钠、无水硫酸镁、无水氯化钙、分子筛中的一种或几种的组合。
5.权利要求2所述荧光分子探针的制备方法，其特征在于：步骤(2)中所用的还原剂为硼氢化钠、氢化铝锂、氢化钙中的一种或者几种。
6.权利要求1中所述的荧光分子探针的应用，其特征在于：用于检测二价铜离子。
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| CN109651319A (zh) * | 2019-01-16 | 2019-04-19 | 许昌学院 | 一种基于香豆素卡巴腙衍生物的荧光探针及其制备方法和应用 |
| CN110818702A (zh) * | 2019-11-22 | 2020-02-21 | 河南理工大学 | 一种吡啶-香豆素衍生物荧光探针及其制备方法和应用 |
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| CN113979996A (zh) * | 2021-10-27 | 2022-01-28 | 济宁医学院 | 用于检测铜离子的邻苯二甲酰亚胺类荧光探针及其制备方法、应用和铜离子的检测方法 |
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| CN109651319A (zh) * | 2019-01-16 | 2019-04-19 | 许昌学院 | 一种基于香豆素卡巴腙衍生物的荧光探针及其制备方法和应用 |
| CN109651319B (zh) * | 2019-01-16 | 2020-10-13 | 许昌学院 | 一种基于香豆素卡巴腙衍生物的荧光探针及其制备方法和应用 |
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